Treatment of hydrocarbon oils



N. S. OLSEN TREATMENT OF HYDROCARBON OILS Filed Aug. 9. 1930 INVENTOR NEAL S. OLSEN Dec. 3, 1935.

Patented Dec. 3, 1935 UNITED STATES PATENT OFFICE mammuor mnocannon ons corporation of South Application August 9, 1930, Serial No. 474,188

Sclaims.

This invention relates to the treatment of hydrocarbon oils and refers more particularly to av process of hydrogenation during the conversion of the hydrocarbon oils.

It is well known that when hydrocarbons are subjected to conversion conditions at elevated temperatures a substantial proportion of the oil is converted into pitchy or even coky material and a substantial portion is converted into gas.

The liquid and solid residues produced by the process have an excess of carbon relative to the hydrogen content, While the gas is usually richer in hydrogen than the original oil treated. It is one of the purposes of the present invention to l5 increase the liquid yield and reducethe formation of carbonaceous and pitchy material by converting the same or preventing their formation by hydrogenation.

As an illustration of the process of the invention reference will be made to the diagrammatic drawing, which is not to scale, and which illustrates one form of apparatus suitable for the process of the invention.

The raw oil charging stock is fed through line I, valve 2, by means of pump 3 through line 4, valve 5, into the dephlegmator 5. A portion or all of the raw oil may be passed directly to the heating element I5 through line 1, valve 8, line 9,1ine I6, valve I1 and line 2 I. The oil entering the dephlegmator 6 is contacted with the vapors arising therein, thereby being heated and in turn condensing a substantial portionof the heavier components of the vapors arising in 6. The reflux condensate together with the raw oil passes through line I0, valve I I and is pumped by means of hot oil pump I2 through line I3, valve I4 into line 9. 'I'he oil passing through line 9 enters the heating element I5 located in furnace setting I5 through' line I6 controlled by valve I1 and through line 2|.

lCatalysts such 'as metals, examples of which are magnesium, aluminum, iron, zinc, tin, cobalt, nickel, chromium and their oxides and salts, preferably in a iinely divided state, may be fed into the heating element I5 through line I8 controlled byvalve I9 by means of pump 20 through line 2| controlled by valve 22. A portion of the oil leaving the heating element I5 alone or in admixture with the catalyst whenused may be recirculated through line 23, valve 24 by means of pump 25 through line 26 'andl valve 21.

T he oil leaving the heating element I5 is passed through line 28 controlled by valve 29 into line 30. Hydrogen or a hydrogen containing gas is introduced into the atomizer through line 32 controlled by valve II and through line 39.

The heated oil in an atomized and vaporized state together with the hydrogen passes from the atomizer 35 through valve 31 into the heating 5 element 38 where it is brought up to a conversion and reaction temperature. The ilow of the oil is controlled by valve 31. A portion of the raw oli or the raw oil mixed with reilux condensate from dephlegmator 6 may be diverted 10 from line 9 through line 38 and valve 39 into line 30 just before entering the atomizer. The purpose of this is mainly for temperature control.

Where the catalyst is not introduced into heating element I5 directly, the mixture oi oil and 1'5 hydrogen may be by-passed after leaving the atomizerv35 through line 4I) controlled by valve 4I into catalytic chamber 42 wherein is placed the afore-mentioned catalyst. lThe catalyst is distributed so as to obtain the maximum con- 20 tact between the mixture of hydrogen and oil and thecatalyst. The mixture leaving the catalytic chamber 42 passes through line 43 controlled by valve 44. Some unvaporlzed residue in catalytic chamber 42 may be withdrawn through line 43' 25 controlled by valve 44'.

A portion of the oil and hydrogen even with the last described operation may be passed through the heating element 36 in order to regulate the temperature of the material leaving the 30 catalytic chamber 42. The oil and unused hydrogen pass through line 45 controlled by valve 46 into reaction chamber 41. Unvaporized liquid residue may be withdrawn from the chamber 41 through line 48 and may be discharged directly 35 for storage through line 49 controlled by valve 50 or a portion of the liquid residue may be passed through line 5 I, valve 52 and pumped by means of pump 53 through line 54, valve 55 into line 9 to be returned to the conversion and reaction zones 40 heretofore described.

The vapors leaving reaction chamber 41 together with unused hydrogen, if any, passes through line 58 and valve 51 into the dephlegmator 6 where they undergo heat exchange with the 45 raw oil and partial condensation.

The vapors leaving dephlegmator 5 pass through line 58 controlled by valve 59 into cooler and condenser 50 and through line'GI, valve 82 into the receiver 63. The low boiling liquid product 50 of the process may be withdrawn through line 54 controlled by valve 85. 'Ihe gases may be removed irom the receiver 59 through line 55 controlled by valve 51. A portion of the liquid withdrawn from receiver 59 through line 59 and valve 55 10 may be recirculated to dephlegmator 6 by means of pump 68 through line 15 controlled by valve 1I.

A portion of the uncondensable gas withdrawn' from receiver 63 through line 18 and valve 19 may be pumped by means of pump 12 through line 'I3 controlled by valve 14 and through line I6, valve I1 and line 2I into the heating element I5.

A portion of the uncondensable gases can be by-passed directly into the atomizer through line 16 controlled by valve 11.

As examples of the operating conditions of my process the pressures upon elements I5 and 36 are preferably maintained quite high and may vary between several hundred pounds per square inch to several thousand pounds more or less. 'I'he temperatures which I prefer in these heating elements are between approximately 800 degrees F., and approximately 1050 degrees F. The pressures upon reaction chamber 41 may be somewhat lower than that utilized for any given operation on heating elements I5 and 36. Differential pressures may be used for the succeeding elements in the system or they may be equalized with respect to reaction chamber 41.

As a specific example of the results obtained by my process, an 18 A. P. I. gravity asphaltic base oil was heated in coil I5 to a temperature of approximately 890 degrees F. About 10% of nely divided iron by weight of the oil was introduced into the heating element together with the oil. A mixture of catalyst and heated oil was discharged into line 30 Where approximately 10% by weight of hydrogen was introduced, the oil, catalyst and hydrogen passing together into the atomizer 35. 'I'he atomized and vaporized oil together with the hydrogen and catalyst enter the conversion coil 36 where the temperature was increased to approximately 935 degrees F. 'I'he pressure maintained upon coil I5 was approximately 1500 pounds per square inch. That maintained upon 36 was equalized with I5 allowing for pressure drops. 'Ihat is this pressure was somewhat lower owing to the friction drop through I 5. The heated mass was then discharged into reaction chamber 41 and subsequently dephlegmated returning the reflux for reconversion, by-passing a portion of the same into line 30 just before the oil and hydrogen entered the atomizer. A portion of the uncondensable gas amounting to approximately 10% by weight ofthe oil was recycled also entering the atomizer. This assisted in atomizing the oil as well as contributing to the hydrogenation,

Approximately of gasoline was made and approximately 25% of a good fuel oil residue. Very little coke was madeduring the operation, combined coke and gas formation based on the weight of the oil being approximately 5% and the remaining was pressure distillate bottoms amounting to approximately 5% or a little over.

In another operation no catalyst was introduced into the heating element I6 the oil being discharged from the heating element together with hydrogen into the atomizer and a portion of the mixture was passed through catalytic chamber 42 5 and the remainder passed through heating element 46. 'I'he conditions of the operation were approximately the same as those above mentioned.

The amounts of material, that is hydrogen and 10 uncondensable gas returned were also approximately the same. The yield of gas was somewhat less than that shown above, the yield of coke somewhat increased and the yield of fuel oil increased. With a gas oil operation the yield of 15 gasoline as high as may be obtained by my process making at the saine time a usable fuel oil residue and very little gas and coke. It is apparent that my process is subject to variable operating conditions. 20

I claim:

1. In the conversion of heavy oils into lower boiling products by hydrogenation, the improvement which comprises heating a mixture of the oil and a finely divided hydrogenating catalyst to 25 cracking temperature under pressure, subjecting the heated mixture to a positive atomizing action with hydrogen, and subjecting said mixture and hydrogen while in atomized condition to between 800 F. and 1050o F. under a pressure in excess 30 of 1000 pounds per square inch.

2. In the conversion of heavy oils into lower boiling products by hydrogenation, the improvement which comprises heating a mixture of the oil and a finely divided hydrogenating catalyst 35 to cracking temperature under pressure, subjecting the heated mixture to a positive atomizing action with hydrogen, and subjecting said mixture and hydrogen while in atomized condition to between 800 F. and 1050 F. under a pressure in 40 excess of 1000 pounds per square inch, fractionating the vapors formed by the hydrogenation to condense heavier fractions thereof, returning resultant reflux condensate to the process adjacent the point of atomization, and finally con- 45 densing the fractionated vapors.

3. In the conversion of heavy oils into lower boiling products by hydrogenation, the improvement which comprises heating a mixture of the oil and a nely divided hydrogenating catalyst to 50 cracking temperature under pressure, subjecting the heated mixture to a positive atomizing action with hydrogen, and subjecting said mixture and hydrogen while in atomized condition to a temperature of at least 800 F. under a pressure in 55 excess of 1000 pounds per square inch, fractionating the hydrogenated vapors and returning resultant reflux condensate to the process adjacent the point of atomization.

NEAL S. OLSEN. 00 

